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Two penta-coordinate complexes of the general formula [Co(Ln)(NCS)]ClO4, where L1 = bis[(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]-[(3,4-dimethoxypyridin-2-yl)methyl]amine and L2 = bis[(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]-[(4-methoxy-3,5-dimethylpyridin-2-yl)methyl]amine, have been synthesized and thoroughly characterized. Each of the cobalt(ii) atoms is penta-coordinated in the CoN5 donor set with a distorted square-pyramidal geometry in [Co(L1)(NCS)]ClO4·MeOH (1), while the vicinity of the central atom can be described as a distorted trigonal-bipyramidal geometry in [Co(L2)(NCS)]ClO4 (2) as revealed using the SHAPE analysis. this website Differences in interatomic parameters among the cobalt(ii) and donor atoms in 1 and 2 have definite impact on the magnetic features of both compounds. The complexes show an easy-axis magnetic anisotropy (D = -38.5 cm-1 for 1 and D = -8.5 for 2), and both complexes reveal a large rhombicity with E/D = 0.21 for 1 and E/D = 0.29 for 2. The ZFS parameters (g, D and E) were also calculated using CASSCF/NEVPT2 methods and they are in good agreement with those determined from experimental data. A frequency dependent out-of-phase susceptibility has been observed in external magnetic field (Bdc = 0.1 T) revealing the following parameters of slow relaxation of magnetization for 1 energy of the spin reversal barrier, Ueff = 16.0 cm-1 (Ueff/kB = 23.0 K) and the relaxation time, τ0 = 1.28 × 10-6 s. In the case of complex 2, no maxima of frequency dependent out-of-phase susceptibility have been observed and thus, the value of Ueff = 17 cm-1 has been estimated using the expression Ueff = |D| × (S2 - 1/4). It has been demonstrated that the degree of substitution and the type of substituents on the pyridyl moieties of the tripodal ligands (L1 and L2) used in these penta-coordinate cobalt(ii) complexes have significant impact on structural and magnetic features.In vitro erythroid cultures from human hematopoietic stem cells produce immature red blood cells (RBCs) called reticulocytes, which are important for RBCs production, and are widely used in scientific studies of malaria pathology, hematological diseases and protein translation. However, in vitro reticulocyte cultures contain expelled cell nuclei and erythroblasts as undesirable by-products and current purification methods such as density gradient centrifugation and fluorescence-activated cell sorting (FACS) are not optimal for integrated bioprocessing and downstream therapeutic applications. Developments in Dean flow fractionation (DFF) and deterministic lateral displacement (DLD) microfluidic sorting methods are ideal alternatives due to label-free size sorting, throughput scalability and low manufacturing cost. DFF sorting of reticulocytes from whole erythroid culture showed a 2.4-fold increase in cell recovery compared to FACS albeit with a lower purity; DLD sorting showed comparable cell recovery and purity with FACS using an inverse-L pillar structure to emphasize size and deformability sorting of reticulocytes. The viability and functional assurance of purified reticulocytes showed conserved cell deformability and supported the propagation of malaria parasites. Collectively, our study on label-free RBCs isolation represents a significant technical advancement towards developing in vitro generated viable human RBCs, opening opportunities for close-loop cell manufacturing, downstream therapeutic and research purposes.This research demonstrates the ability to direct the rate and extent of lipid hydrolysis of oleogels using a combination of different structuring agents. Combinations of ethyl cellulose (EC) (20 cP and 45 cP) and commercial mixture of mono and di-glycerides (E471), at different ratios, were examined. The results suggest that the combination of E471 and EC significantly affects both gel physical properties and intestinal lipolysis. The gelation profile of the combined system demonstrated the EC sol-gel transition, which is characterized by G' = G'' at high temperatures (∼100 °C) followed by a soft-to-hard gel transition at low temperatures ∼30 °C, which corresponds to E471 crystallization. Such a profile suggests the formation of two gel networks, with the polymer network acting as a platform for E471 crystallization. Mechanical analysis reveals harder gels in the E471  EC 20 cP mixture compared with the simple addition of each component contribution, suggesting a synergistic effect with a typical maximum at 7  3 E471  EC 20 cP ratio. No significant additive effect was observed for E471  EC 45 cP mixtures. Maximum lipolysis in the order of EC less then E471  EC less then E471 was obtained, implying an effect of the structuring agent used on the lipolysis profile. A first-order kinetics analysis fitted to the lipolysis profiles demonstrated rate constant values in the order of E471 less then E471  EC less then EC. Such behavior was attributed to the oil state, liquid vs. solid, and the network strength, both of which limit the lipase activity by hindering liquid TAG accessibility. Overall, the results demonstrate the ability to control gel properties and hydrolysis by manipulating gel composition. Such rational design can be exploited when developing new fat mimetic systems aimed at controlling the lipid digestion profile or the release of hydrophobic components present in the oil phase.Membranes are crucial to lowering the huge energy costs of chemical separations. Whilst some promising polymers demonstrate excellent transport properties, problems of plasticisation and physical aging due to mobile polymer chains, amongst others, prevent their exploitation in membranes for industrial separations. Here we reveal that molecular interactions between a polymer of intrinsic microporosity (PIM) matrix and a porous aromatic framework additive (PAF-1) can simultaneously address plasticisation and physical aging whilst also increasing gas transport selectivity. Extensive spectroscopic characterisation and control experiments involving two near-identical PIMs, one with methyl groups (PIM-EA(Me2)-TB) and one without (PIM-EA(H2)-TB), directly confirm the key molecular interaction as the adsoprtion of methyl groups from the PIM matrix into the nanopores of the PAF. This interaction reduced physical aging by 50%, suppressed polymer chain mobilities at high pressure and increased H2 selectivity over larger gases such as CH4 and N2.
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